Apparatus and method for recovery of acetic acid from an aqueous solution thereof

ABSTRACT

The invention disclosed relates to an apparatus and method for recovering acetic acid from an aqueous feed stream containing acetic acid, in particular a stream generated during terephthalic acid production. The apparatus includes: a liquid-liquid extraction column to which water-rich feed streams are fed, having a guard bed situated near the top and within the extraction column for conversion by reaction with acetic acid of alcohol within the mixture to the corresponding ester; and an azeotropic distillation column to remove residual water from acetic acid, to which water-poor feed streams are fed directly at a height of the azeotropic distillation column at which the mixture therein has a similar water concentration. The liquid-liquid extraction column produces an extract comprising an extraction solvent and acetic acid which is sent to the azeotropic distillation column to separate residual water and acetic acid.

BACKGROUND OF THE INVENTION

The invention relates generally to reduction of energy consumption in chemical processes used in the distillation of industrial chemicals, and in particular to distillation systems and methods for the recovery of acetic acid from aqueous solutions. The present invention is particularly suited for the recovery of acetic acid used in the production of terephthalic acid.

Terephthalic acid is useful in a diverse variety of industrial applications and chemical processes. For example, terephthalic acid is a starting material for producing polyesters including plastic and Dacron™ polyester used in textile and container production. Polyethylene terephthalate (PET) is a form of polyester or Mylar™ that is an extremely tough resin and useful in many industrial and consumer applications. Soft drink and water bottles are made from this resin in addition to plastic jars and clamshell packages used in consumer good transport and food distribution. Purified terephthalic acid is a higher grade of terephthalic acid which is used for finer industrial applications.

Terephthalic acid typically is produced by reaction of paraxylene with molecular oxygen in the presence of a catalyst. During the production process, acetic acid is used as a solvent of terephthalic acid. The acetic acid becomes diluted in water during the oxidation in a reactor section of a terephthalic acid plant in the production cycle. A portion of the acetic acid and water containing stream is then sent to a dehydration unit to remove the water generated in the reactor for recycling or waste.

Three different approaches have been employed in the terephthalic acid plants to separate the acetic acid and water so that the acetic acid can be recycled back to the reactor while the water generated by the reaction is sent to the wastewater treatment facility for safe disposal. One approach is by conventional distillation wherein the different boiling point of the components provides for the separation of acetic acid and water. In an azeotropic distillation approach, entrainers are used to form azeotropes with the acetic acid and water providing for a change in energy requirements for processing. Liquid-liquid extraction is a final approach for acetic acid and water separation during the terephthalic acid production.

Distillation has been widely used as a primary unit operation for acetic acid recovery from water. In such processes, one or more towers are utilized to process a number of streams of varying concentrations of acetic acid with the purpose of recovering it for further use in the oxidation reactor. The products from the distillation tower are a bottom stream of concentrated acetic acid and an overhead stream that ideally would be pure water to minimize the loss of the valuable acetic acid solvent. A more pure overhead water stream would also reduce the burden on downstream wastewater treatment facilities thereby preventing accidental chemical spills.

However, the distillation of acetic acid and water is not very efficient due to the close-boiling characteristics of the acetic acid/water system. Conventional distillation systems require the use of high number of theoretical stages, i.e., actual trays, and a high reflux ratio, i.e., high energy consumption, to obtain reasonably low levels of acetic acid, typically in the range of 0.5-0.8wt % in the overhead distilled water. The distillate is subsequently processed to recover certain organic by-products, and then sent to the wastewater treatment facility where any remaining acetic acid is neutralized and spent.

The use of conventional distillation, therefore, involves high investment cost because of the required large size of equipment and high operating cost because of high steam consumption. Furthermore, the traditional process scheme does not allow one to economically obtain a distillate low in acetic acid concentration. This limitation, in turn, presents operating problems including costs associated with the operation resulting from the acetic acid losses, costs associated with the treatment of the acetic acid in the wastewater, limitations of the capacity of the downstream wastewater treating facility and environmental problems that are continually increasing because of the ever more rigorous standards for acceptable levels of emission to the environment.

There has been an effort to look for alternative processes to minimize the high operating costs associated with the conventional distillation for the separation of acetic acid and water. Chemical processors and companies have resorted to azeotropic distillation involving the addition of selective alkyl acetate, such as the isobutyl acetate, normal butyl acetate, normal propyl acetate, etc., as a entrainer to the azeotropic dehydration column. The entrainer forms a low boiling azeotrope with water and therefore improves the relative volatility for the separation between the acetic acid containing stream and the alkyl-acetate/water azeotrope. This reduces the energy and theoretical stage requirements for the same separation. Compared to the conventional distillation, an azeotropic distillation approach typically reduces the energy (i.e., steam) consumption by 20-40% at the acetic acid/water dehydration column while giving relatively low acetic acid concentration, 300-800 ppm, in the distilled water. The azeotropic distillation column is generally operated at ambient pressure in the terephthalic acid manufacturing plants in all prior art systems.

Other methods used in terephthalic acid production includes the use of liquid-liquid extraction with special extractive agents to recover the acetic acid from the water streams so that the residual concentration is reduced to 0.1 wt % to 2.0 wt % acetic acid. Some of the agents usually used are acetates, amines, ketones, phosphine oxides, and mixtures thereof. These agents are used as solvent such that they dissolve one component preferentially, allowing the other component to leave at the top of the extraction column. Once the extraction step is completed, a complicated series of distillation steps is required to recover the acid and to recirculate the solvent back to the extraction column.

Such extraction and azeotropic distillation processes for recovery of acetic acid from aqueous streams are described by, for example, Othmer in U.S. Pat. No. 2,395,010 (1946) and Sasaki et al. in U.S. Pat. 5,662,780 (1997), and have been applied to recovery of acetic acid from manufacture of terephthalic acid as described, for example, by Ohkoshi et al. in Japanese Patent Application JP 244196/95 (1995); also European Patent Application EP 0 764 627.

However, these processes are still energy intensive, and it is desirable to further reduce energy consumption in recovery of acetic acid from such streams.

SUMMARY OF THE INVENTION

According to the invention, an extraction and distillation apparatus for recovering acetic acid from an aqueous solution thereof e.g. during terephthalic acid production is disclosed comprising, an extraction column, an azeotropic distillation column for dehydration of the extractant, and a plurality of input feed streams containing various concentrations of acetic acid and water mixtures. The extraction column is a liquid-liquid contacting device and is located upstream from and in fluid communication with the azeotropic distillation column.

In one embodiment, the new apparatus also includes separate locations for feed streams into the azeotropic distillation and liquid-liquid extraction columns, respectively, for the different water-poor (below about 50%) and water-rich (above about 50%) streams containing acetic acid.

In another embodiment, a guard bed is provided within the extraction column.

In yet another embodiment, the new apparatus further comprises a pre-concentrator for providing more concentrated aqueous acetic solutions to both the liquid-liquid extractor and the azeotropic distillation column.

According to a process aspect of the invention, the aqueous stream fed into the extraction column is contacted with an extraction solvent into which acetic acid is extracted thus substantially reducing the concentration of acetic acid in the water stream. Preferably, the extraction solvent is selected from a group of isobutyl acetate, normal butyl acetate, isopropyl acetate, and ethyl acetate. An azeotropic mixture comprising water and, preferably, an ester that is the same ester as the extraction solvent is distilled from the top of the azeotropic distillation column, and an acetic acid rich liquid stream is recovered from the bottom of said azeotropic distillation column.

It has also been found that there is a tendency for the concentration of the alcohol produced by hydrolysis of the ester to build up during operation of the process, necessitating either separation or destruction of said alcohol, thereby reducing the overall efficiency of the process and increasing costs of operation.

Accordingly, a guard bed is installed in the extraction column to prevent build up of the amount of alcohol that is hydrolyzed from the acetates in the process. The alcohol is esterified in the guard bed to the corresponding acetate, thus keeping the alcohol content, and therefore the acetate content in the process at a constant level, improving the efficiency of the separation process.

In another embodiment of the invention, water-poor and water-rich streams are fed at different locations of the liquid/liquid extraction column, to improve the efficiency of the separation process and thereby reduce energy consumption.

In yet another embodiment, water-poor streams are fed directly to the azeotropic distillation column, each stream being fed at a height in said column at which the aqueous mixture within said column has a similar water concentration.

The net effects of incorporating one or more of these features, preferably together, are to improve the overall efficiency of the process for separation and recovery of acetic acid from aqueous streams, to substantially reduce energy consumption for the overall terephthalic acid production processes.

Further, the distillation apparatus and process described herein are compatible with existing terephthalic acid manufacturing systems so that the invention may be readily installed to enhance existing plants without large capital expenditures.

These and other goals and embodiments of the invention will be better appreciated and understood when considered in conjunction with the following description and the accompanying drawings. It should be understood, however, that the following description, while indicating multiple embodiments of the invention and numerous specific details thereof, is given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the invention without departing from the spirit thereof, and the invention includes all such modifications.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an illustrative flow sheet for a PRIOR ART process using acetates for separation by azeotropic distillation of water from acetic acid containing streams.

FIG. 2 illustrates a flow diagram of an acetic acid dehydration system according to the invention, incorporating both a guard bed within the extraction column and having two sites for feeding water-poor and water-rich streams at different locations of the azeotropic distillation column.

FIG. 3 illustrates a flow diagram for a terephthalic acid manufacturing facility having a water concentrator for production of a stream richer in acetic acid for further processing to recover said acetic acid, wherein the liquid and vapor from the concentrator are respectively fed to the extraction and the azeotropic distillation column as shown in FIG. 2. Optionally, a flash drum is included to partly volatolize acetic acid.

DETAILED DESCRIPTION OF THE INVENTION

Herein, conventional tower internals refers to various types of trays, packings and the like. Conventional distillation refers to a conventional distillation tower without the use of entrainers or solvents in the separation of the chemicals. Azeotropic distillation refers to a distillation tower and process utilizing an entrainer to separate the chemicals. An entrainer is a mass separating agent used to separate a mixture by forming a lower boiling azeotrope with at least one of the components in that mixture in this case, an azeotropic mixture of water and the entrainer.

What is needed is a more energy efficient distillation system for recovery of acetic acid from streams also containing water, which produces less waste and unwanted byproducts than prior art systems. Preferably, the distillation system and process should be compatible with existing terephthalic acid manufacturing systems so that it may be readily installed to enhance existing plants without large capital expenditures.

All liquid streams, without limitation to acetic acid concentration, can be sent to the liquid-liquid extractor, whereas vapor streams which cannot be fed to the liquid-liquid extraction column are sent directly to the azeotropic column.

Large amounts of energy are expended within prior art systems for recovery of acetic acid from aqueous streams effluent from processes for production of terephthalic acid.

An exemplary process for production of terephthalic acid is shown in prior art FIG. 1, taken from Jang et al., U.S. Pat. 7,048,835 B2 (2006). In addition to the energy expenditures at such plants, minimal to no recycling occurs where solvents such as acetic acid are not recovered and are sent to wastewater treatment facilities, thereby increasing the energy requirements by requiring further processing outside the scope of the plant system.

There are several streams of effluent 74 a, 74 b, 74 c, 74 d, 74 e containing both water and acetic acid emanating from terephthalic acid production facilities, as illustrated in FIG. 1, including relatively water-poor streams (water content up to about 50%) 74 a, 74 b, 74 c and water-rich streams (water content typically over 50%) 74 d, 74 e. Water-poor streams 74 a, 74 b, 74 c are drawn from reactor condensers and crystallizers/solvent strippers. Water-rich streams 74 d, 74 e are drawn from absorbers, and include the water draw distillate and the wash water from press filters.

Referring again to FIG. 1, while it is possible to use an azeotropic distillation column 14 alone to partly separate water and acetic acid, for example by use of an alkyl-acetate entrainer to form an acetate-water azeotrope, this method has high demand for energy and is less efficient than other methods, especially for high water concentration streams.

Terephthalic acid typically is produced by reaction of para-xylene with molecular oxygen in the presence of catalysts, in a system such as, for purpose of illustration, that illustrated in FIG. 1, taken from U.S. Pat. 7,048,835 B2 (2006) by Jang et al., and the process described by Ohkoshi et al. in Japanese Patent Application JP 244196/95 (1995) and European Patent Application EP 0 764 627 (1996). There are several different examples of such processes, the essential components of which may be common to different manufacturing plants. During the production process, acetic acid is used as a solvent of terephthalic acid. The acetic acid becomes diluted in water generated during the oxidation reaction in a reactor of the terephthalic acid plant. A portion of the resulting aqueous acetic acid stream is then sent to the azeotropic distillation column (dehydration unit, not illustrated) to remove the water generated in the reaction for recycling or waste.

Typically there are the following aqueous acetic acid streams for feeding to an azeotropic distillation column (dehydration unit): stream 1, condensates from oxidation reactor condensers; stream 2, vapor or condensates from 1^(st) and 2^(nd) crystallizer; stream 3, solvent stripper OVHD vapor; and stream 4, bottom liquid from high pressure and atmospheric absorbers.

The acetic acid in the streams which contain less than 50 wt % acetic acid can be extracted by liquid-liquid extraction with a solvent, one example of such a process is described by Sasaki et al in U.S. Pat. No. 5,662,780 (1997) in which only one liquid feed with acetic acid concentration 10-50 wt % is allowed to be fed to the liquid-liquid extractor with a solvent 24, which is also used as an entrainer for azeotropic distillation.

Among the above streams, stream 2 includes over 80 wt % of acetic acid and its temperature is too high to send it to extractor 12. As stream 3 is vapor phase, it cannot be sent to extractor 12. Stream 4 contains less than 50 wt % acetic acid and its temperature is lower than 50° C., and so it can be sent to extractor 12. The resulting acetic acid rich solution in the extract 28 then can be separated using azeotropic distillation.

In the case of stream 1, the apparatus for the oxidation process for production of terephthalic acid has typically 3˜4 condensers. The condensates from the 1^(st) and 2^(nd) condensers 78 a, 78 b contain over 80 wt % of acetic acid, and their temperature is over 160° C. The condensates from the 3^(rd) and 4^(th) condensers 78 c, 78 d contain 70˜80 wt % of acetic acid and their temperature is 50˜70° C.

Less than 50 wt % of acetic acid from condensate from oxidation reactor 76 can be recovered by installing a distillation tower, the water concentrator 90 after the 2^(nd) condenser.]

As shown in FIG. 3, overhead vapor from the oxidation reactor is condensed in the 1^(st) condenser and 2^(nd) condenser. The condensate is recycled back to reactor 76 as reflux and non-condensed vapor is fed to the bottom of the water concentrator 90. The bottom liquid from the water concentrator 90 is recycled to reactor 76 and overhead vapor is sent to 3^(rd) and 4^(th) condensers. A portion of the condensate (about 50 wt % acetic acid) 80 is sent to extractor 12, as illustrated in FIG. 2, and the rest is recycled back to the water concentrator 90 as reflux. Non-condensed vapor 82 is sent to the high pressure absorber.

As will be described below, extraction solvent 24 is recoverable during further processing for reuse in extraction column 12, to which it may be fed in combination with stream 20.

Referring to FIG. 2, extraction-azeotropic distillation systems 38 for recovery of acetic acid from aqueous solutions from terephthalic acid plants includes an extraction column 12 and an azeotropic distillation column 14. All aqueous acetic acid feed streams at an acetic concentration of 35% may be combined into a single feed stream 16 and fed into extraction column 12 at a site close to the top of said column 12. The extractor shown in FIG. 3 indicates two feed streams at two different concentrations. The invention allows for multiple feeds to the extractor, at different locations based on feed stream acetic acid concentrations.

As seen in FIG. 2, optionally a flash drum 66 may be included for phase separation of an acetic acid rich stream 68 into acetic acid vapor 70 and liquid 71. Acetic acid rich liquid 71 can be fed to top of extractor 12 while the vapor 70 can be combined with vapor feed stream 72 and fed directly to azeotropic distillation column 14.

Acetic acid is extracted from feed streams 16 and 73 into extraction solvent 24, thus greatly depleting the concentration of acetic acid in the aqueous component of the mixture in extraction column 12. An acetic acid-depleted aqueous stream 26 exits the bottom of extraction column 12 for further treatment before disposal. The resulting solution 28 containing extraction solvent 24 and acetic acid exits the top of extraction column 12 and toward azeotropic distillation column 14. Solution 28 typically also contains lesser amounts of water and, when extraction solvent 24 is an ester, the corresponding alcohol formed from hydrolysis of said ester (e.g. isopropyl alcohol from isopropyl acetate, or normal butyl alcohol from normal butyl acetate), and may contain other contaminants. Build up of the alcohol and other contaminants is undesirable as they diminish the efficiency of the overall acetic acid recovery process and increase costs resulting from consumption of materials to form waste and necessary purification of effluent streams before disposal.

As seen in FIG. 2, Additional water-poor feed streams are fed directly to the azeotropic distillation column at different heights in said column at which the aqueous mixture within said column has a similar water concentration.

Solution 28 is fed into an azeotropic distillation column 14 where it is distilled to separate the majority of the remaining water from the acetic acid. An entrainer 30 is fed near the top of azeotropic distillation column 14. Entrainer 30 forms an azeotropic mixture 32 with water so that said azeotropic mixture 32 is distilled from the top of said column 14. Preferably, entrainer 30 and extraction solvent 24 are the same chemical, and more preferably that chemical is selected from among lower-alkyl esters e.g. normal butyl acetate, isobutyl acetate, normal propyl acetate and isopropyl acetate. An acetic acid rich and water-poor liquid stream 36 is recovered from the bottom of azeotropic distillation column 14.

Azeotropic mixture 32 is condensed and forms two liquid phases which can be separated in a decanter into a water-rich phase which can be further treated before disposal, and a water-poor phase comprising mostly entrainer 30/extraction solvent 24 which can be recycled as stream 22 and reused in extraction column 12, as shown in FIG. 2.

Referring to FIGS. 1 and 2, the deficiencies inherent in prior art acetic acid recovery processes are addressed according to the apparatus and process according to the invention Common features of prior art apparatus 10 and new apparatus 38 will be identified using the same reference numerals for like parts.

Referring to FIG. 2, in one aspect of the present invention, a guard bed 40 is situated close to the top within extraction column 12. Guard bed 40 contains an esterification catalyst 42 over which acetic acid reacts with alcohol present in the reaction mixture to form the corresponding ester, as illustrated in Equation 1 for the case of normal butyl acetate. Guard bed 40 effects reduction of the amount of alcohol circulating in the system. Alcohol tends to build up during operation of the process. Build up of the amount of alcohol present in the system compromises efficiency of the process through affecting various components: separation of the mixture by distillation in azeotropic distillation column 14; the composition of the azeotrope distilled; and extraction of acetic acid using the entrainer in extraction column 12. Thus operation of each of the major components of the apparatus is deleteriously affected by alcohol build up. Incorporation of guard bed 40 to control alcohol build up thus allows more continuous operation of apparatus 10 in the manner for which it is designed.

Guard bed 40 is situated near the top of extraction column 12 as that is where the concentration of alcohol is highest and the concentration of water is lowest within said column 12, thus favoring ester formation. When guard bed 40 is installed within extraction column 12 the amount of alcohol built up within the system is lower than that in prior art systems. It is an advantage to combining the esterification process and the extraction process within one column 12 to reduce the number of vessels, thus reducing the capital costs and the footprint of the plant, and to thereby treat feed from the extractor directly upon entry into extraction column 12.

In contrast to the present invention, Sasaki et al. in U.S. Pat. No. 5,662,780 (1997) use an external guard bed because the terephthalic acid process for which their invention is designed differs from other terephthalic acid processes in that it has only one aqueous feed stream. Generally, all other terephthalic acid manufacturing plants have multiple aqueous acetic acid containing streams from different parts of the plant. Thus, for all these other plants, application of the Sasaki '780 invention would require combining of these various streams, which is disadvantageous when compared to the present invention. Combining the acetic acid containing aqueous streams would result in a diluted stream having over 50% water, and so more energy would be required to effect the separation of water and acetic acid from each other.

Reaction 1 is accelerated by using an acidic catalyst such as alumina-HZSM5 or acidic forms of ion exchange resins, for example Amberlyst® 36. The equilibrium shown in Equation 1 lies to the right, as shown from thermodynamic data (Table 1). The reduction in alcohol content achieved through use of the guard bed within the extraction column is illustrated in Table 2.

n-C₄H₉OH+HOAc←→n-C₄H₉OAc+H₂O  (1)

TABLE 1 Thermodynamic data for hydrolysis of normal butyl acetate (reverse of Eq. 1). Temperature ΔH ΔS ΔG (° C.) (kcal) (cal/° C.) (kcal) K Log(K) 50 0.632 0.428 0.493 4.64E-01 −0.334 65 0.808 0.961 0.483 4.87E-01 −0.312

TABLE 2 Reduction in concentration of normal butyl alcohol through esterification with acetic acid Component Feed (wt %) Product (wt %) Case 1: Temperature 50° C., high alcohol content n-BuOAc 50 67.8 n-BuOH 30 18.7 H₂O 10 12.8 HOAc 10 0.823 Case 2: Temperature 65° C., high alcohol content n-BuOAc 50 67.7 n-BuOH 30 18.7 H₂O 10 12.7 HOAc 10 0.861 Case 3: Temperature 50° C., moderate alcohol content n-BuOAc 70 80.2 n-BuOH 10 3.49 H₂O 10 11.6 HOAc 10 4.73 Case 4: Temperature 65° C., moderate alcohol content n-BuOAc 70 80.0 n-BuOH 10 3.59 H₂O 10 11.6 HOAc 10 4.81

From Table 2 it can be seen that esterification by reaction with acetic acid greatly reduces the amount of alcohol present in the mixture, thus providing a more appropriate mixture from which acetic acid is extractable under the designed conditions.

Referring to FIG. 1, in another aspect of the present invention, advantage is taken of the different concentrations of water present in different effluent streams originating from the terephthalic acid manufacturing process. Water-rich streams from terephthalic acid plant components: absorbers, water draw distillate and wash water from the press filter(s), may be combined and are fed near the top of extraction column 12.

Water-poor streams from terephthalic acid plant components: water drawn from reactor condensers and from crystallizer(s)/solvent strippers, are fed separately to azeotropic distillation column 14. Beneficially, each water-poor stream is fed at a height 50 a, 50 b, 50 c within azeotropic column at which the water concentration is similar to that of the stream, thus minimizing energy requirements to effect the separation of water and extraction solvent 24 containing acetic acid.

The advantages of implementation of the first and second innovations together are:

to reduce the energy required to effect separation of acetic acid from the aqueous feed and to process water before discharging;

to improve the efficiency of operation of the separation process by reducing the amount of undesirable alcohol circulating within the system and so maintain the composition of the mixtures circulating within the apparatus at reasonably consistent levels so as to most closely match the parameters at which the apparatus is designed to operate; and

to reduce the amount of waste requiring extraction or destruction before wastes can be eliminated from the plant.

The net effect is a more economical and environmentally more friendly process than prior art systems. The utility and energy savings derived from application of the present invention have been determined, and are summarized in Table 3.

A further advantage of the present invention is that the distillation apparatus and process described herein are compatible with existing terephthalic acid manufacturing systems so that they may be readily installed to enhance existing plants without large capital expenditures. Catalyst bed 40 is readily installed into extraction column 12. Feed lines for different streams can be installed at the appropriate locations in azeotropic distillation column 14 without compromising components already in place.

TABLE 3 Comparison of steam consumption for different acetic acid recovery processes. Azeotropic Description Conventional Distillation Distillation Sasaki's Patent Invention Entrainer No No Yes Yes Yes Yes Extraction Solvent No No No Yes Yes Yes Steam Consumption* 100 125 70 55 90 55 Acetic Acid 7000 1000 1000 1000 1000 1000 Concentration in Waste No of Feeds to Multiple Multiple Multiple Single Single Multiple Dehydration System Feed Condition Liquid and Liquid and Liquid and Liquid only Liquid only Liquid and Vapor Vapor Vapor Vapor Feed Composition No Limit No Limit No Limit Limited to <50 wt Not effective No Limit Limititation % Acetic Acid when Acetic Recommended Feed 5 wt %~90 wt % 5 wt %~90 wt % 5 wt %~90 wt % 10 wt %~50 wt % Acid >50 wt % 5 wt %~90 wt % Composition Acetic Acid Acetic Acid Acetic Acid Acetic Acid Acetic Acid *Calculated based on identical combined feed rates and acetic acid concentration (at 70 wt %) to the Dehydration system.

It is noteworthy that, as shown in Table 3, the present invention affords operating benefits and cost savings over all prior art processes for recovery of acetic acid from aqueous streams, and in particular for recovery of acetic acid from effluent streams from terephthalic acid manufacturing processes. The steam demand for conventional distillation methods is much higher than that from the present invention, and this is especially so when it is required that the concentration of acetic acid in wastewater is to be no greater than 1000 ppm. Similarly, azeotropic distillation to separate water and acetic acid without prior extraction in an extraction column also requires higher steam demand. The process described by Sasaki et al. in '780 has similar steam demand to that of the present invention, but only when the feed is in the liquid phase and contains less than 50% acetic acid, which does not represent all the acetic acid streams encountered in a typical PTA plant. On the other hand, using the Sasaki's scheme for liquid feed with acetic acid concentration comparable with other cases, i.e., 70 wt %, the process of Sasaki et al. has a higher steam demand. There is no other process described that combines the range of feeds that can be processed and the energy efficiency of the present invention.

Optionally, further benefit can be gained through an additional modification, useful independently of the above innovations, and even more useful when used in combination with therewith. The apparatus shown in FIG. 3 is modified as follows. The aqueous effluent stream from second distillation/condensation column 78 b of the terephthalic acid manufacturing plant, is sent first to a water concentrator 90. A stream richer in acetic acid then is directed to the extractor (extraction column 12, FIG. 2) for extraction of acetic acid and subsequent processing as described above.

The foregoing description of preferred embodiments of the invention is presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in this art. It is intended that the scope of the invention be defined by the following claims and their equivalents.

References Cited

U.S. Patent Documents 7,048,835 B2 May, 2006 Jang et al. 203/16 5,662,780 September, 1997 Sasaki et al. 203/81 2,395,010 February, 1946 Othmer 260-541 U.S. Patent Applications PCT/US2006/036963 September, 2005 Jang and Wu Foreign Patents and Applications EP 0 764 627 A1 March, 1997 Ohkoshi et al. (JP 244196/95 (1995)) 

1. An apparatus for recovering acetic acid from an aqueous solution thereof, comprising: a liquid/liquid extraction column, an azeotropic distillation column in fluid communication therewith and located downstream thereof, means for feeding into the extraction column an input feed stream containing organics, acetic acid and water, means for feeding into the extraction column an extraction solvent into which acetic acid is extracted to reduce the concentration of acetic acid in the feed stream, resulting in water-poor and water-rich fractions at the top and bottom of the extraction column, respectively, means for feeding the water-poor fraction into the azeotropic distillation column, means for feeding an entrainer into the azeotropic distillation column, and means for recovering from the top of the column, an azeotropic mixture including water and the entrainer, and from the bottom of the column an acetic acid-rich liquid stream.
 2. An apparatus according to claim 1, additionally comprising a guard bed containing a catalyst for esterification of alcohol by reaction with acetic acid to form the corresponding ester, situated within and near the top of the extraction column.
 3. An apparatus according to claim 2 wherein the input feed stream is a plurality of liquid feed streams of different acetic acid concentrations, wherein all or portions of the liquid input streams, contain acetic acid concentrations of 5-90 wt %, preferably 5-80 wt %.
 4. An apparatus according to claim 3, wherein additional water-poor feed streams are fed directly to the azeotropic distillation column, each stream being fed at a height in said column at which the aqueous mixture within said column has a similar water concentration.
 5. An apparatus according to claim 4, wherein the extraction solvent is a lower-alkyl acetate selected from the group consisting of isobutyl acetate, normal butyl acetate, isopropyl acetate and normal propyl acetate.
 6. An apparatus according to claim 5, wherein the entrainer is a lower-alkyl acetate selected from the group consisting of isobutyl acetate, normal butyl acetate, isopropyl acetate and normal propyl acetate.
 7. An apparatus according to claim 6, wherein the entrainer is the same as an extraction solvent used in the extraction column.
 8. An apparatus according to claim 7, wherein the azeotropic mixture is fed to a condenser, and a portion of the condensate, typically <60%, preferably 10-50% of the total condensate, is returned to the extraction column as an extraction solvent.
 9. An apparatus according to claim 8, wherein the input feed stream is aqueous acetic acid effluent from a production facility for manufacture of terephthalic acid.
 10. An apparatus according to claim 9, wherein the catalyst for esterification of an alcohol is an acidic catalyst selected from the group consisting of acid forms of aluminosilicate and acid forms of ion exchange resins.
 11. An apparatus according to claim 2, additionally comprising a pre-concentrator and a high pressure absorber, wherein the aqueous acetic acid feed stream is pre-concentrated in a water concentrator, and a vapor fraction from the water concentrator is partially condensed, and a vapor fraction is fed to the high pressure absorber, and a portion of a liquid fraction is sent to the liquid-liquid extractor, while the remainder of the liquid fraction is returned to the water concentrator as a reflux.
 12. An apparatus according to claim 2, additionally comprising a flash drum, wherein at least one aqueous acetic acid input stream is flashed in the flash drum, and: a liquid fraction is fed to the liquid-liquid extractor, and a vapor fraction is fed to the azeotropic distillation column.
 13. A method for recovering acetic acid from an aqueous solution thereof, comprising, providing an extraction column and an azeotropic distillation column in fluid communication therewith and located downstream thereof, feeding into the extraction column, an input stream comprising acetic acid, organics and water, feeding into the extraction column an extraction solvent into which acetic acid is extracted to reduce the concentration of acetic acid in the feed stream, resulting in water-poor and water-rich fractions at the top and bottom of the extraction column, respectively, feeding the water-poor fraction to the azeotropic distillation column, feeding an entrainer into the distillation column and running the distillation column, and recovering from the top of the column, an azeotropic mixture including water and the entrainer, and from the bottom of the column an acetic acid-rich liquid stream.
 14. A method according to claim 13, additionally comprising providing a guard bed located within and near the top of the extraction column containing a catalyst for esterification of alcohol, wherein alcohol by reaction with acetic acid forms the corresponding ester.
 15. A method according to claim 14, comprising before feeding to the liquid/liquid separator, pre-concentrating the aqueous acetic acid solution.
 16. A method according to claim 15, wherein the extractant solvent is a lower-alkyl ester, selected from the group consisting of isobutyl acetate, normal butyl acetate, isopropyl acetate and normal propyl acetate.
 17. A method according to claim 16, wherein the entrainer is an ester, selected from the group consisting of isobutyl acetate, normal butyl acetate, isopropyl acetate and normal propyl acetate.
 18. A method according to claim 17, wherein additional water-poor feed streams are fed directly to the azeotropic distillation column, each stream being fed at a height in said column at which the mixture within said column has a similar water concentration.
 19. A method according to claim 18, wherein the catalyst for esterification of an alcohol is an acidic catalyst selected from the group consisting of acid forms of aluminosilicate and acid forms of ion exchange resins.
 20. A method according to claim 19, wherein the input feed stream is a plurality of liquid feed streams of different acetic acid concentrations, wherein all or portions of the liquid input streams, contain acetic acid concentrations of 5-90 wt %, preferably 5-80 wt %. 